AU2004255863A1 - Process for the preparation of furopyrroles - Google Patents
Process for the preparation of furopyrroles Download PDFInfo
- Publication number
- AU2004255863A1 AU2004255863A1 AU2004255863A AU2004255863A AU2004255863A1 AU 2004255863 A1 AU2004255863 A1 AU 2004255863A1 AU 2004255863 A AU2004255863 A AU 2004255863A AU 2004255863 A AU2004255863 A AU 2004255863A AU 2004255863 A1 AU2004255863 A1 AU 2004255863A1
- Authority
- AU
- Australia
- Prior art keywords
- alkyl
- formula
- hydrogen
- group
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims description 32
- 238000002360 preparation method Methods 0.000 title claims description 18
- -1 cyanomethyl Chemical group 0.000 claims description 97
- 229910052739 hydrogen Inorganic materials 0.000 claims description 55
- 239000001257 hydrogen Substances 0.000 claims description 53
- 125000000217 alkyl group Chemical group 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 38
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 38
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 30
- 229910052736 halogen Inorganic materials 0.000 claims description 27
- 150000002367 halogens Chemical class 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 23
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims description 9
- 239000012442 inert solvent Substances 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 150000003141 primary amines Chemical class 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 7
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000001246 bromo group Chemical group Br* 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 125000004414 alkyl thio group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 5
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000004457 alkyl amino carbonyl group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 claims description 4
- 125000002883 imidazolyl group Chemical group 0.000 claims description 4
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 4
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 125000003172 aldehyde group Chemical group 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 3
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 claims description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000000468 ketone group Chemical group 0.000 claims description 3
- 125000002757 morpholinyl group Chemical group 0.000 claims description 3
- 150000002825 nitriles Chemical class 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000002971 oxazolyl group Chemical group 0.000 claims description 3
- 125000004193 piperazinyl group Chemical group 0.000 claims description 3
- 125000003386 piperidinyl group Chemical group 0.000 claims description 3
- 125000000719 pyrrolidinyl group Chemical group 0.000 claims description 3
- 125000005401 siloxanyl group Chemical group 0.000 claims description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 125000001425 triazolyl group Chemical group 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical group ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 12
- 150000001266 acyl halides Chemical class 0.000 claims 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 38
- 239000000203 mixture Substances 0.000 description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 22
- 239000002904 solvent Substances 0.000 description 22
- 239000007787 solid Substances 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- 239000000049 pigment Substances 0.000 description 11
- 238000007639 printing Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- 239000000976 ink Substances 0.000 description 8
- 230000005855 radiation Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- DENKGPBHLYFNGK-UHFFFAOYSA-N 4-bromobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Br)C=C1 DENKGPBHLYFNGK-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229910000104 sodium hydride Inorganic materials 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- 125000005907 alkyl ester group Chemical group 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 5
- YVTXDUDNQBZRSI-UHFFFAOYSA-N ethyl 3-(4-bromobenzoyl)-2-oxo-5-phenyl-1,3-dihydropyrrole-4-carboxylate Chemical compound CCOC(=O)C1=C(C=2C=CC=CC=2)NC(=O)C1C(=O)C1=CC=C(Br)C=C1 YVTXDUDNQBZRSI-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- HSHBOGFNJZVMSG-UHFFFAOYSA-N 1-(4-bromophenyl)-4-phenyl-5h-furo[3,4-c]pyrrole-3,6-dione Chemical compound C1=CC(Br)=CC=C1C(OC1=O)=C2C1=C(C=1C=CC=CC=1)NC2=O HSHBOGFNJZVMSG-UHFFFAOYSA-N 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- GLOUXWJKUPSJRH-UHFFFAOYSA-N ethyl 2-oxo-1,5-diphenyl-3h-pyrrole-4-carboxylate Chemical compound O=C1CC(C(=O)OCC)=C(C=2C=CC=CC=2)N1C1=CC=CC=C1 GLOUXWJKUPSJRH-UHFFFAOYSA-N 0.000 description 4
- 239000003630 growth substance Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical class C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 4
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 description 4
- 239000012312 sodium hydride Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- MHCVCKDNQYMGEX-UHFFFAOYSA-N 1,1'-biphenyl;phenoxybenzene Chemical compound C1=CC=CC=C1C1=CC=CC=C1.C=1C=CC=CC=1OC1=CC=CC=C1 MHCVCKDNQYMGEX-UHFFFAOYSA-N 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical compound C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 3
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 3
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 3
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- NRQZZIYLLBKCFC-UHFFFAOYSA-N ethyl 3-benzoyl-2-oxo-1,5-diphenyl-3h-pyrrole-4-carboxylate Chemical compound CCOC(=O)C1=C(C=2C=CC=CC=2)N(C=2C=CC=CC=2)C(=O)C1C(=O)C1=CC=CC=C1 NRQZZIYLLBKCFC-UHFFFAOYSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- QKFKNXHPCNWQDQ-UHFFFAOYSA-N 1,2,4,5-tetraphenylpyrrolo[3,4-c]pyrrole-3,6-dione Chemical compound C=12C(=O)N(C=3C=CC=CC=3)C(C=3C=CC=CC=3)=C2C(=O)N(C=2C=CC=CC=2)C=1C1=CC=CC=C1 QKFKNXHPCNWQDQ-UHFFFAOYSA-N 0.000 description 2
- PKQYSCBUFZOAPE-UHFFFAOYSA-N 1,2-dibenzyl-3-methylbenzene Chemical compound C=1C=CC=CC=1CC=1C(C)=CC=CC=1CC1=CC=CC=C1 PKQYSCBUFZOAPE-UHFFFAOYSA-N 0.000 description 2
- OIAQMFOKAXHPNH-UHFFFAOYSA-N 1,2-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 OIAQMFOKAXHPNH-UHFFFAOYSA-N 0.000 description 2
- CNBTVZNEASNWOQ-UHFFFAOYSA-N 1,4,5-triphenylfuro[3,4-c]pyrrole-3,6-dione Chemical compound C=12C(=O)OC(C=3C=CC=CC=3)=C2C(=O)N(C=2C=CC=CC=2)C=1C1=CC=CC=C1 CNBTVZNEASNWOQ-UHFFFAOYSA-N 0.000 description 2
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical compound C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 2
- LXKMRQZLXSTWLZ-UHFFFAOYSA-N 1-(4-bromophenyl)-5-methyl-4-phenylfuro[3,4-c]pyrrole-3,6-dione Chemical compound CN1C(=O)C2=C(C=3C=CC(Br)=CC=3)OC(=O)C2=C1C1=CC=CC=C1 LXKMRQZLXSTWLZ-UHFFFAOYSA-N 0.000 description 2
- QCYIIUQCOIMIJB-UHFFFAOYSA-N 1-(4-nitrophenyl)-4-phenyl-5h-furo[3,4-c]pyrrole-3,6-dione Chemical compound C1=CC([N+](=O)[O-])=CC=C1C(OC1=O)=C2C1=C(C=1C=CC=CC=1)NC2=O QCYIIUQCOIMIJB-UHFFFAOYSA-N 0.000 description 2
- LOTKRQAVGJMPNV-UHFFFAOYSA-N 1-fluoro-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C([N+]([O-])=O)=C1 LOTKRQAVGJMPNV-UHFFFAOYSA-N 0.000 description 2
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- MPQXYKMGVONCKS-UHFFFAOYSA-N 5-methyl-1-(4-nitrophenyl)-4-phenylfuro[3,4-c]pyrrole-3,6-dione Chemical compound CN1C(=O)C2=C(C=3C=CC(=CC=3)[N+]([O-])=O)OC(=O)C2=C1C1=CC=CC=C1 MPQXYKMGVONCKS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 150000001351 alkyl iodides Chemical class 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 2
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- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DMDPGPKXQDIQQG-UHFFFAOYSA-N pentaglyme Chemical compound COCCOCCOCCOCCOCCOC DMDPGPKXQDIQQG-UHFFFAOYSA-N 0.000 description 1
- 125000005327 perimidinyl group Chemical group N1C(=NC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000004934 phenanthridinyl group Chemical group C1(=CC=CC2=NC=C3C=CC=CC3=C12)* 0.000 description 1
- 125000004625 phenanthrolinyl group Chemical group N1=C(C=CC2=CC=C3C=CC=NC3=C12)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000001042 pteridinyl group Chemical group N1=C(N=CC2=NC=CN=C12)* 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004627 thianthrenyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3SC12)* 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
Description
WO 2005/005430 PCTIEP2004/051259 1 Process for the Preparation of Furopyrroles The present invention relates to a microwave assisted rapid and economical process for the preparation of furopyrroles of the general formula 1, comprising (a) heating a compound of 5 the formula II under microwave irradiation optionally in the presence of an inert solvent. The furopyrroles of the general formula I can be obtained in high yield and high purity by the process of the present invention. W003022848 discloses a process for the preparation of furopyrroles of the general formula I, 10 comprising heating a compound of the formula
A
1
CO
2 R H-N OH (Ila) in an inert solvent, 0 A 2 wherein A' and A 2 have the meanings as given below and R is Cl-C 16 alkyl, in particular C
C
4 alkyl, aryl, in particular phenyl, or aralkyl, in particular benzyl, which can be substituted one to three times with C-Csalkyl, C 1 -Csalkoxy, or halogen. Examples of inert solvents include, 15 but are not limited to, aromatic solvents, like biphenyl, para-, meta or ortho-terphenyl, dibenzyltoluene, a-methyl- or p-methylnaphthalene, cyclic carbonates, like 1,3-dioxolan-2 one, ketones, like acetophenone or benzophenone, y-butyrolactone and ethylene glycols, like Phe-Cellosolve or Bu-Cellosove, or mixtures thereof, in particular mixtures of di- and triarylethers (Dowtherm A@). 20 It has now surprisingly been found, that the 3,6-diphenylfuro[3,4-c]pyrroe-1,4-diones (furopyrroles) of formula I can be obtained in higher yield by carrying out the above reaction under microwave radiation. The yield of the ring closure of ethyl 4-benzoyl-4,5-dihydro-5-oxo 2-phenylpyrrole-3-carboxylate to 3,6-diphenylfuro[3,4-c]pyrrole-1,4-dione is, for example, 25 increased from 40 to 86 % by the microwave assisted process according to the present invention. Moreover, we have observed that the preparation of this lactone (a versatile DPP precursor) requires lesser time (1 to 10 minutes) under microwave irradiation while ring closure of the compound of formula 11 takes 60 hours when conducted without microwave radiation (conventional method). In addition, the solvent can be omitted in the microwave 30 assisted ring closure, which makes the above process further cost effective.
WO 2005/005430 PCT/EP2004/051259 2 Accordingly, the present invention relates to a process for the preparation of furopyrroles of Ai O the general formula A-N O (l), comprising 0
A
2 (a) heating a compound of the formula A
CO
2 R A-N OH (11) under microwave irradiation optionally in the presence of an inert 0 A 2 5 solvent, wherein A' and A 2 are Cl-C 18 alkyl, C 2
-C
1 alkenyl, C 2
-C
18 alkynyl, C 6 -Cacycloalkyl, C6 Cgcycloalkenyl, aryl or heteroaryl,
A
3 is hydrogen, Cl-CBalkyl, cyanomethyl, Ar, -CRaoR 31
-(CH
2 )m-Ar 3 or Y-R 3 2 , wherein R 3 0 and
R
3 1 independently of each other stand for hydrogen or C-C 4 alkyl, or phenyl which can be 10 substituted up to three times with Cl-C 4 alkyl, Ar 3 stands for aryl, C 5 -Cscycloalkyl, C 5 -Cecycloalkenyl or heteroaryl, which can be substituted one to three times with C-C 8 alkyl, Cj-C 8 alkoxy, halogen or phenyl, which can be substituted with C-Caalkyl or C-Cealkoxy one to three times, and m stands for 0, 1, 2, 3 or 4, R is Cl-C 18 alkyl, in particular C-C 4 alkyl, aryl, in particular phenyl, or aralkyl, in particular 15 benzyl, which can be substituted one to three times with C-C 8 alkyl, C 1
-C
8 alkoxy, or halogen, Y is -C(O)-, -C(0)0-, -C(O)NH-, -SO 2 NH- or -SO 2 - and
R
3 is C-C, 8 alkyl, Ar 3 , or aralkyl. If desired, the process of the present invention can be carried out in the presence of an inert solvent. Examples of inert solvents include, but are not limited to, aromatic solvents, like 20 biphenyl, para-, meta or ortho-terphenyl, dibenzyltoluene, a-methyl- or p-methylnaphthalene, cyclic carbonates, like 1,3-dioxolan-2-one, ketones, like acetophenone or benzophenone, 'y butyrolactone and ethylene glycols, like Phe-Cellosolve or Bu-Cellosove, or mixtures thereof, in particular mixtures of di- and triarylethers (Dowtherm A@). In a preferred embodiment the compound of the formula I is heated for about 1 to 60 25 minutes at a temperature of 180 to 280 "C, preferably 180-230 *C, with or without solvent, under microwave irradiation.
WO 2005/005430 PCT/EP2004/051259 3 A microwave furnace suitable for the irradiating the composition comprises a microwave source, microwave frequency range selector, a microwave frequency modulator to modulate the microwave frequency across the selected frequency range, microwave forward power controller to select the forward power setting, a thermocouple, an infrared temperature 5 sensor or other temperature measuring means, and a microwave forward power on/off controller to turn the forward power on and off in response to the temperature of the composition. Frequency modulation increases the uniformity of the power distribution throughout the furnace cavity, thereby heating the composition uniformly. Suitable microwave furnaces are described in, for example, U.S. Pat. Nos. 5,321,222 and 5,961,871 to Bible et 10 al., U.S. Pat. No. 5,648,038 to Fathi et al., and U.S. Pat. No. 5,521,360 to Johnson et al. A presently preferred microwave furnace is commercially available from CEM, Inc., as model Discover@. The Discover@ System incorporates temperature and pressure feedback systems, for example, an infrared temperature sensor positioned below the reaction vessel, for complete control of the reaction. 15 It is preferred that the reaction mixture be irradiated in a vessel transparent to microwave radiation in the frequency range employed. The samples, comprising the compounds of formula Il and optionally the solvent, are advantageously heated in pressurized tubes, such as, for example, sealed glass tubes, whereby the pressure is allowed to increase up to 25 a 106 Pa. Preferably the pressure is 20 between I to 14 - 105 Pa. The selection of the actual microwave frequency range will depend on the reactants, but will generally be about 0.9 to about 2.45 GHz. Selection of a forward power input will depend on the nature of the reactants. For example, in the synthesis of 3-(p-bromophenyl)-6-phenyl furo[3,4-c]pyrrole-1,4-dione, a preferred forward power level is about 150 to 300 watts. 25 As described in W003022848 the furopyrroles of formula I can be used as crystal growth regulators and are intermediates in the synthesis of diketopyrrolopyrroles, which can be obtained by reacting a compound of formula I with a primary amine of the formula A 4
-NH
2 A 0 424 (IV), wherein a DPP of formula As -N N-A4 (Ill) is obtained, 0 A 2 wherein A 4 is C-C, 8 alkyl or Ar 3 , and Al, A 2 and A 3 are as defined above. 30 The reaction between the compound of the general formula I and the primary amine or the mixture of primary amines is carried out in a suitable inert solvent or dispersant.
WO 2005/005430 PCT/EP2004/051259 4 Suitable solvents or dispersants are, for example, ethers, in particular those having 2 to 8 carbon atoms in the molecule, such as, for example, diethyl ether, methyl ethyl ether, di-n propyl ether, diisopropyl ether, methyl n-butyl ether, methyl tert-butyl ether, ethyl n-propyl ether, di-n-butyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, bis-B 5 methoxyethyl ether; oligoethylene glycol dimethyl ethers, such as, for example, pentaglyme; aliphatic hydrocarbons, such as, for example, hexane, heptane, low- and high-boiling petroleum ethers; cycloaliphatic hydrocarbons, such as, for example, cyclohexane, methylcyclohexane, tetralin, decalin; aromatic hydrocarbons, such as, for example, benzene, toluene, o-, m- and p-xylene, ethylbenzene; halogenated aliphatic or aromatic hydrocarbons, 10 such as, for example, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene; nitriles, such as, for example, acetonitrile; amides, such as, for example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone; hexamethyl phosphoric triamide; and sulfoxides, such as, for example, dimethyl sulfoxide. Mixtures of various solvents can also be used. 15 The reaction is preferably carried out in a dipolar or non-polar aprotic solvent. Examples of preferred aprotic solvents are: dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, sulfolane, N-methylpyrrolidone, tetramethylurea, acetonitrile, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether, nitromethane, 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone 20 (DMPU), 1,3-dimethyl-2-imidazolidinone, benzonitrile, nitrobenzene, chloroform, carbon tetrachloride and methylene chloride. Particularly preferred aprotic solvents are chloroform, carbon tetrachloride and methylene chloride, of which chloroform is particularly preferred. The reaction between the compound of the general formula I and the primary amine IV is carried out in the presence of a dehydrating agent. Examples of suitable dehydrating or 25 water-eliminating agents of this type are: N,N'-disubstituted carbodiimides, in particular if they contain at least one secondary or tertiary alkyl radical, such as, for example, diisopropyl-, dicyclohexyl- or N-methyl-N'-tert.-butylcarbodiimide (cf. "The Chemistry of Ketenes, Allenes and Related Compounds", Part 2, Editor: S. Patai, John Wiley & Sons 1980, 722-753). Dicyclohexylcarbodiimide is particularly suitable. 30 The reaction between the compound of the formula I and the primary amine IV can be carried out, for example, at temperatures from -10* C up to the boiling point of the solvent or solvent mixture used. In many cases it is carried out at -10 to 30 "C and preferably at room temperature. 0.9 to 1.4 mol, preferably 1.0 to 1.3 mol of the primary amine IV are in general employed per mole of compound of the general formula 1. The reaction can be catalyzed by 35 adding a strong non-aqueous acid such as trifluoroacetic acid.
WO 2005/005430 PCT/EP2004/051259 5 The primary amines IV are known or can be easily prepared by the methods known for the preparation of these class of compound. The starting compound of the formula la, wherein A 3 is different from a hydrogen atom, is obtained by reacting a compound of the formula Ai 0 5 H-N 0 (la) with a compound of the formula A -X (V), wherein A', A 2 and 0 A 2
A
3 have the meanings as given above and X is a leaving group. The reaction between the compound of the general formula la and the compound of the formula V is carried out in a suitable inert solvent such as tetrahydrofuran, in the presence of a base such as sodium hydride (NaH) or sodium hexamethyldisilazane (NaHMDS), at a temperature ranging from 20 10 *C to the boiling point of the solvent. The term "leaving group" means a group, such as iodo, bromo or chloro, benzene- or p-toluenesulfonate. Processes for the introduction of A 3 into compounds of the formula la are described, for example, in US-A-4,585,878. Suitable alkylating agents are, for example, alkyl halides, in particular alkyl iodides, reactive alkyl esters, in particular alkyl esters of sulfonic acids, such as, for example, alkyl esters of 15 benzene- or p-toluenesulfonic acid. Suitable arylating agents are for example activated aryl compounds such as 1-fluoro-2,4-dinitro-benzene. The starting compound of the formula Ila is obtained by reacting a compound of the formula A
CO
2 R H-N (Vla) with an ester of the formula A 2
-CO
2 R (VII) in the presence of a 0 base, such as for example NaH or NaHMDS at a temperature ranging from 25 "C to the 20 boiling point of the solvent, wherein R, A' and A 2 have the meanings as given above. The starting compounds of the formula VI are known or can be prepared in analogy to processes described in US-A-4,681,971, US-A-4,749,795, US-A-4,720,305 and US-A 4,659,775. Alternatively, compounds of the formula WO 2005/005430 PCT/EP2004/051259 6
A
1
CO
2 R A'--N (VIl1), wherein A 3 is different from a hydrogen atom and is in particular 0 aryl, can be prepared by a copper catalyzed decomposition of diazoacetates in the presence of enaminoamides (G. Maas, A. Mller, J. prakt. Chem. 340 (1998) 315-322): 1 3 CO 2 R A CONHA3 N2=C-CO 2 R Ai silica gel N H CONHA3 , VIII Cu(acac) 2 NHf/H20 00 5 In addition, compounds of formula (VIII) wherein A 3 is aryl can be obtained by reacting a compound of formula (lIb) with an amine A 3
-NH
2 : A CO 2 R
A
1
CO
2 R A -NH 2 / o 0 (1Ib) (VIII). Preferably, the lactone of formula (11b) is reacted with aniline to afford the N-phenyl 10 pyrrolinone ester of formula (VIlI) as described in more detail in Example 4. The compounds of the formula VI, wherein A 3 is different from a hydrogen atom and is in particular aryl, can be reacted to compounds of the formula III as described above.
WO 2005/005430 PCT/EP2004/051259 7
A
1
CO
2 R A CO2R
A
2
-CO
2 R C A'_-N A_-N OH 0 (Vill) 0 (l) t AT A O A 0 4 A4-NH2 AL-N
N-A
4
-
2 As-N 0 0 A 2 (011) 0 A 2 (I) In addition, DPP of formula (Ill) wherein A' and A 2 are C-C, 8 alkyl, C 2
-C
1 8 alkenyl, C 2 C 1 8 alkynyl, C 5 -Cacycloalkyl, C 5
-C
8 cycloalkenyl, aryl or heteroaryl,
A
3 is hydrogen, CI-C 18 alkyl, cyanomethyl, Ar 3 , -CR 3 0
R
3 1
-(CH
2 )m-Ar 3 or Y-R , wherein R 3 0 and 5 R 31 independently of each other stand for hydrogen or Cr-C 4 alkyl, or phenyl which can be substituted up to three times with C-C 4 alkyl, ArP stands for aryl, C 5
-C
8 cycloalkyl, C 5 -Cacycloalkenyl or heteroaryl, which can be substituted one to three times with C-C 8 alkyl, C-Caalkoxy, halogen or phenyl, which can be substituted with Cl-Caalkyl or C-Csalkoxy one to three times, and m stands for 0, 1, 2, 3 or 4, 10 R is C-C 18 alkyl, in particular CI-C 4 alkyl, aryl, in particular phenyl, or aralkyl, in particular benzyl, which can be substituted one to three times with C-C 8 alkyl, C 1
-C
8 alkoxy, or halogen, Y is -C(O)-, -C(0)O-, -C(O)NH-, -SO 2 NH- or -S0 2 -,
R
3 is C-C 18 alkyl, Ar 3 , or aralkyl, and
A
4 is hydrogen 15 can also directly be obtained by reacting a compound of formula (VIII) with a nitrile A2 -CN, wherein A', A 2 and A 3 have the meanings as given above:
A
1
A
1 O
CO
2 R N t-AmONa
A
3 -N + t-AmOH A 3 -N NH
A
2 (l0
A
2 (Vill) (I11).
WO 2005/005430 PCT/EP2004/051259 8 Further, the compound of the formula Ill can be reacted with a compound of the formula
A
5 -X, wherein A 5 has the meaning of A 3 as given above and X is a leaving group. The reaction between these compounds is carried out in a suitable inert solvent such as tetrahydrofuran, in the presence of a base such as sodium hydride (NaH) or sodium 5 hexamethyldisilazane (NaHMDS), at a temperature ranging from 20 "C to the boiling point of the solvent. The term "leaving group" means a group, such as iodo, bromo or chloro, benzene- or p-toluenesulfonate. Suitable alkylating agents are, for example, alkyl halides, in particular alkyl iodides, reactive 10 alkyl esters, in particular alkyl esters of sulfonic acids, such as, for example, alkyl esters of benzene- or p-toluenesulfonic acid. Suitable arylating agents are for example activated aryl compounds such as 1-fluoro-2,4-dinitro-benzene. One preferred embodiment concerns DPPs of general formula Ill wherein residues A' and A 2 15 are different from phenyl. The DPPs of the general formula Ill show a high heat stability, a good solubility in polymers, hydrocarbon based fuels, lubricants, and water, a high light stability, and the ability to be used in plastics, especially polyamides, without decomposition and loss of lightfastness, and 20 in paints; and can show photo- and electroluminescence as well as solid state fluorescence. The residues A' and A 2 are in general selected from C-Casalkyl, C 2
-C
18 alkenyl, C 2 C 1 8 alkynyl, C 5 -Cacycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, in particular cyclohexyl, C 5 -Cecycloalkenyl, such as cyclopentenyl, cyclopentadienyl and cyclohexenyl, in particular cyclohex-3-enyl, aryl and heteroaryl. 25 Diketopyrrolopyrroles, wherein A' and A 2 are radicals of the formula R2 R 2,NN WO 2005/005430 PCT/EP2004/051259 9 R5 R 4 0 or G R 3 , wherein
R
6 R' and R 2 are independently of each other hydrogen, halogen, C-C 16 alkyl, C-C 18 alkoxy, C
C
18 alkylmercapto, di(C 1
-C
18 alkyl)amino, Cr-C 18 alkylamino, C-C 1 alkoxycarbonyl, C
C
18 alkylaminocarbonyl, -CN, -NO 2 , trifluoromethyl, C 5 -Cecycloalkyl, -C=N-(C-C 18 alkyl), R 4 5 phenyl, -C=N /3 , imidazolyl, pyrrazolyl, triazolyl, piperazinyl, pyrrolyl, oxazolyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, morpholinyl, piperidinyl or pyrrolidinyl, -CONX 5
X
6 , -C(O)OX 7 or -SO 2
X
9 ; wherein X 5 and X 6 are hydrogen, linear or branched Cl-lo-alkyl, C- 10 -cycloalkyi or C 6
.
1 0 -aryl, X 7 is hydrogen, linear or branched
C
1 oo-alkyl, C- 10 -cycloalkyl or CO 10 -aryl, X 9 is hydrogen, linear or branched CI 1 0 -alkyl, C51o 10 cycloalkyl, C 7
.
1 0 -aralkyl, C 6 1 0 -aryl or -NX 10
X
11 , wherein X 1 0 and X" are hydrogen, linear or branched C1 1 o-alkyl, C 7 10 -aralkyl or Co 1 0 -aryl, G is -CH 2 -, -CH(CH 3 )-, -C(CH 3
)
2 -, -CH=N-, -N=N-, -0-, -S-, -SO-, -S02-, -CONH- or -NR 7 -,
R
3 and R4 are independently of each other hydrogen, halogen, Cl-C 6 alkyl, Cl-C 18 alkoxy or CN, R 5 and RG are independently of each other hydrogen, halogen or C-C 6 alkyl, and R 7 is 15 hydrogen or C-C 6 alkyI are preferred, wherein radicals of the formula R _CN R/~N , or R2 R4 G R3 wherein R 1 and R 2 are independently of each other hydrogen, chloro, bromo, CI-C 4 alkyl, Cl-C 6 alkoxy, C-C 6 alkylamino, phenyl or CN, 20 G is -0-, -NR 7 -, -N=N- or -S02-,
R
3 and R 4 are hydrogen, and WO 2005/005430 PCT/EP2004/051259 10
R
7 is hydrogen, methyl or ethyl are further preferred and diketopyrrolopyrrole analogues, wherein A' and A 2 are radicals of the formula R -02 R wherein R 1 and R 2 are independently of each other hydrogen, methyl, tert-butyl, chloro, 5 bromo, phenyl or CN are particularly preferred for the preparation of inks, colorants, pigmented plastics for coatings, non-impact-printing material, color filters, cosmetics, polymeric ink particles, toners. In the case of electroluminescence applications the following residues are preferred for A' 10 and A 2 :
R
2 6 I -6 -26
R
2 5 R 21 R R1 R23 R N1 R R 2 R 2 2 ( N R 2, R R N R N R R ~ R 23 R N 3 R 211 2212 R R R 23 R N R 2 R RN R R RR22 R 21 2R R 1R23 R N3 R 2 RN R R R 2 R
R
2 3
R
2 1
R,
22 15R22 1R23 WO 2005/005430 PCT/EP2004/051259 11 R 5R22 R 2R2 R R R5 O 2 23 N R 26 R N R 23 R 2 R 21 R 23 or RR
R
24 N R 26 wherein R 21 , R2, R 23 , R" and R 2 ' are independently of each other hydrogen, C 1
-C
8 alkyl, a hydroxyl group, a mercapto group, C-Csalkoxy, C 1
-C
8 alkylthio, halogen, halo-C-Csalkyl, a 5 cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group, a silyl group or a siloxanyl group and
R
24 is a 0 1 -Calkyl group. Preferably R 21 , R2, R 23 , R 25 and R 26 are independently of each other hydrogen, C-Csalkyl, C-Csalkoxy or C-Cealkylthio, wherein the following residues are particularly preferred: 10 N N WO 2005/005430 PCT/EP2004/051259 12 N N N N K- N N or/H3 The residue A 3 is in general selected from hydrogen, CI-C 1 salkyl, cyanomethyl, Ar, 5 -CR3R 3 1
-(CH
2 )m-Ar 3 or Y-R 32 , wherein R 30 and R 3 1 independently of each other stand for hydrogen or C-C 4 alkyl, or phenyl which can be substituted up to three times with C-C 3 alkyl, Ar 3 stands for aryl, in particular phenyl or 1- or 2-naphthyl, C 6
-C
8 cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, in particular cyclohexyl, C 5 C 8 cycloalkenyl, in particular cyclopentenyl, cyclopentadienyl and cyclohexenyl, or heteroaryl, 10 which can be substituted one to three times with C-Caalkyl, C-Cealkoxy, halogen or phenyl, which can be substituted with Cj-C 8 alkyl or Cl-Caalkoxy one to three times, and m stands for 0, 1, 2, 3 or 4, Y is -C(O)-, -C(O)O-, -C(O)NH-, -SO 2 NH- or -SO 2 - and R 32 is C-C 18 alkyl, Ar 3 , or aralkyl. 15 A 3 is preferably hydrogen, C 1
-C
8 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.
butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, Y-R 3 2 wherein Y is -C(O)- and R 3 2 is 0 - R 40, wherein R40 is Cl-C 4 alkyl, -O-C-C 4 alkyl, or -S-Ci-C 4 akyI and
-(CH
2 )m-Ar wherein m is I and Ar is a group of the formula WO 2005/005430 PCT/EP2004/051259 13 or which can be substituted one to three times with C-C 8 alkyl, C-C 8 alkoxy, halogen or phenyl. Examples of preferred residues Ar are 5 0 5 R 51
R
50 or R 5 wherein R" and R6' are independently of each other methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, methoxy, ethoxy, isopropoxy, tert.-butoxy or chlorine. The residue A 4 is in general selected from C-C 1 3alkyl or ArP, in particular Ar 3 , wherein A 4 is preferably 10 or which can be substituted one to three times with C-Caalkyl, C-Cealkoxy, halogen or phenyl. The furopyrroles of the formula I are intermediates in the process for the preparation of the diketopyrrolopyrroles of the formula Ill and, as described in W003022848, can be used as 15 crystal growth regulators, wherein the term "regulating the crystal growth" refers to controlling the synthesis of pigment particles to have a suitable pigmentary size and/or a narrow particle size distribution as well as directing the growth of the crystals to generate particles of a specifically desired shape, such as platelet, needle, cubic, leaflet, prismatic and other geometric forms and/or of a specifically desired rheology. Consequently, the better control of 20 the crystal growth affords samples with a narrower particle size distribution and/or a better crystal shape, or both. The effect can be influenced by the chemical structure of the organic pigment, the selection of the reaction media and the concentration and chemical structure of the inventive particle growth regulator. 25 If used as crystal growth regulator the furopyrroles of the formula I are present in amount of from about 0.1-20%, especially from 1.0 to 10.0%, based on primary pigment weight. Although DPPs are preferred as primary pigment, the use of diverse pigment moieties is likewise available where the respective pigments are color compatible.
WO 2005/005430 PCT/EP2004/051259 14 Examples of applicable organic primary pigments are: anthraquinone, phthalocyanine, perinone, perylene, dioxazine, diketopyrrolopyrrole, thioindigo, isoindoline, isoindolinone, quinacridone, quinacridonequinone, flavanthrone, indanthrone, anthrapyrimidine or quinophthalone pigments, and solid solutions comprising these pigments. Preferred organic 5 pigments are quinacridones, phthalocyanines, anthraquinones, perylenes, diketopyrrolopyrroles, isoindolinones and indanthrones. When the pigment compositions are prepared, the diketopyrrolopyrrole analogues of the formula I can be added during the pigment synthesis, during the fine dispersion process, before or after a finishing process by methods well-known in the art (cf. W003022848). 10 Furopyrroles of the formula I, wherein A' and A 2 are radicals of the formula R/ R/\N ,N , R2 R 2 \_ O or G - R 3 , wherein
R
6 15 R' and R 2 are independently of each other hydrogen, halogen, C-C 18 alkyl, Cr-C 18 alkoxy, C
C
18 alkylmercapto, C 1
-C
1 8 alkylamino, C-CiBalkoxycarbonyl, C 1
-C
1 8 alkylaminocarbonyl, -CN, NO 2 , trifluoromethyl, C 5 -CBcycloalkyl, -C=N
R
4
(C-C
18 alkyl), phenyl, -C=N /6R , imidazolyl, pyrazolyl, triazolyl, piperazinyl, pyrrolyl, oxazolyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, morpholinyl, 20 piperidinyl or pyrrolidinyl, -CONX 5
X
6 , -C(O)OX 7 , -SX 9 , -SOX 9 , or -S0 2
X
9 ; wherein X 5 and X6 are hydrogen, linear or branched C 1
.
10 -alkyl, Co 10 -cycloalkyl or Cs.
1 0-aryl, X is hydrogen, linear or branched C 11 -alkyl, Cs.
10 -cycloalkyl or Cs.
10 -aryl, X9 is hydrogen, linear or branched
C
1
.
1 3-alkyl, C5.
1 o-cycloalkyl, C 7
.
10 -aralkyl, C.
10 -aryl or -NX' X", wherein X 1 0 and X" are hydrogen, linear or branched C 1 .1 0 -alkyl, C 7
_
1 o-aralkyl or Cs.
10 -aryl, WO 2005/005430 PCT/EP2004/051259 15 G is -CH 2 -, -CH(CH 3 )-, -C(CH 3 )2-, -CH=N-, -N=N-, -0-, -S-, -SO-, -S 0 2-, -CONH- or -NR 7 -,
R
3 and R 4 are independently of each other hydrogen, halogen, C-C 6 alkyl, Cr-C 1 8 alkoxy or CN, R 5 and R 6 are independently of each other hydrogen, halogen or C-C 6 alkyl, and R 7 is hydrogen or C-C 6 alkyl are preferred, wherein radicals of the formula R CN 5 R \ , N , or 2 R4 G R 3 wherein R 1 and R 2 are independently of each other hydrogen, chloro, bromo, C-C 4 alkyl, Cl-C 6 alkoxy, C-C 6 alkylamino, phenyl or CN, -CONXX 6 , -SX 9 , -SOX9, or -SO 2
X
9 ;or -SO 2
X
9 ; wherein X 5 and X 6 are hydrogen, linear or branched C-alkyl, X' is hydrogen, linear or 10 branched C 1
.
1 8 -alkyl, C 7
.
1 0 -aralkyl, CO.
1 0 -aryl or -NX 0 X", wherein X' 0 and X" are hydrogen, linear or branched C 110 -alkyl, C 7
_
1 0 -aralkyl or C 6 1 0 -aryl; G is -0-, -NR 7 -, -N=N-, -S-, -SO- or -S02-,
R
3 and R 4 are hydrogen, and
R
7 is hydrogen, methyl or ethyl are further preferred and diketopyrrolopyrrole analogues, 15 wherein A' and A 2 are radicals of the formula R R , -2 R or wherein R 1 and R2 are independently of each other hydrogen, C 1 4 -alkyl, such as methyl or tert-butyl, halogen, such as chloro or bromo, C 1 4 -alkoxy or C-thioalkyl, phenyl or CN or
-SO
2
X
9 , wherein X9 is C 1
.
4 -alkyl, phenyl, benzyl or NX 1 0 X", wherein X 1 0 and X" are 20 hydrogen, C 1 4 -alkyl, benzyl or phenyl are particularly preferred.
A
3 is preferably hydrogen, C 1
-C
8 alkyI such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.
butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, Y-R32 wherein Y is -C(O)- and R 32 is WO 2005/005430 PCT/EP2004/051259 16
R
40 , wherein R40 is C-C 4 alkyl, -O-C-C 4 alkyl, or -S-C-C 4 alkyl and
-(CH
2 )m-Ar wherein m is I and Ar is a group of the formula or which can be substituted one to three times with C-C 8 alkyl, Gl-CBalkoxy, halogen or phenyl. 5
C-C
1 8 alkyl is typically linear or branched - where possible - and examples of CC 1
-
8 alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3 pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2 ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl 10 and octadecyl. CI-Cealkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl is preferred. Cr-C 4 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl or tert.-butyl is particularly preferred. The term
"C
2
-C
18 alkenyl group" means an unsaturated linear or branched aliphatic hydrocarbon group 15 containing one or more double bonds, in particular C 2 8 -alkenyl, such as vinyl, allyl, 2-propen 2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl, 2-methyl-I buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl and 1,4-pentadien-3-yl. The term
"C
2 -ClEalkynyl group" means an unsaturated aliphatic hydrocarbon group containing a triple bond, in particular C 2
-C
8 -alkynyl such as ethynyl, 1-propyn-1-yl, 2-butyn-1-yl, 3-butyn-1-yl, 20 2-pentyn-1-yl and 3-pentyn-2-yl. Examples of Cl-C 1 1alkoxy, which can be linear or branched, are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, 2,2-dimethylpropoxy, n-hexoxy, n-heptoxy, n-octoxy, 1,1,3,3-tetramethylbutoxy and 2 ethylhexoxy, wherein C-C 4 alkoxy such as methoxy, ethoxy, n-propoxy, isopropoxy, 25 n-butoxy, sec.-butoxy, isobutoxy and tert.-butoxy is preferred. Examples of Cl-C 18 alkylmercapto are the same groups as mentioned for the alkoxy groups, except that the oxygen atom of the ether linkage is replaced by a sulphur atom. Examples and preferences for C-C 1 salkyl in CI-ClBalkylamino and Cl-C 1 alkylaminocarbonyl are the same as mentioned for C-C 18 alkyl. Examples and preferences for Cl-C 18 alkoxy in 30 C-C 18 alkoxycarbonyl are the same as mentioned for C-C 18 alkoxy. The term "aryl group" is typically C 6
-C
2 4 aryl, such as phenyl, 1 -naphthyl, 2-naphthyl, 4 biphenyl, phenanthryl, terphenyl, pyrenyl, 2- or 9-fluorenyl or anthracenyl, preferably Ca- WO 2005/005430 PCT/EP2004/051259 17
C
1 2 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, which may be unsubstituted or substituted. The term "aralkyl group" is typically C 7
-C
24 aralkyl, such as benzyl, 2-benzyl-2-propyl, phenylethyl, a,a-dimethylbenzyl, o&-phenylbutyl, o, o-dimethyl-o-phenylbutyl, 5 o-phenyldodecyl, oephenyloctadecyl, co-phenyleicosyl or cnphenyldocosyl, preferably
C
7
-C
18 aralkyl such as benzyl, 2-benzyl-2-propyl, p-phenylethyl, a,a-dimethylbenzyl, co-phenylbutyl, co, codimethyl-o-phenylbutyI, o-phenyldodecyl or o-phenyloctadecyl, and particularly preferred C 7
-C
12 aralkyl such as benzyl, 2-benzyl-2-propyl, p-phenyl-ethyl, a,a-dimethylbenzyl, o-phenyl-butyl, or o,wdimethyl-o-phenyl-butyl, in which both the 10 aliphatic hydrocarbon group and aromatic hydrocarbon group may be unsubstituted or substituted. Examples of C 5
-C
8 cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, which may be unsubstituted or substituted. The term "C 5 -Cecycloalkenyl group" means an unsaturated alicyclic hydrocarbon group containing one or more double bonds, such as 15 cyclopentenyl, cyclopentadienyl and cyclohexenyl, which may be unsubstituted or substituted. The term "heteroaryl" is a ring with five to seven ring atoms, wherein nitrogen, oxygen or sulfur are the possible hetero atoms, and is typically an unsaturated heterocyclic radical with five to 18 atoms having at least six conjugated g-electrons such as thienyl, benzo[b]thienyl, 20 dibenzo[b,d]thienyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, quinolyl, isoquinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, 25 perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl or phenoxazinyl. Examples of a halogen atom are fluorine, chlorine, bromine and iodine. If the above-mentioned substituents can be substituted, possible substituents are Cl-C 8 alkyl, a hydroxyl group, a mercapto group, C-Caalkoxy, C-Coalkylthio, halogen, halo-C-C 8 alkyl, a 30 cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group, a silyl group or a siloxanyl group. As described in W003022848 the DPPs of the general formula Ill can be used for the preparation of 35 inks for printing inks in printing processes, for flexographic printing, screen printing, packaging printing, security ink printing, intaglio printing or offset printing, for pre-press WO 2005/005430 PCT/EP2004/051259 18 stages and for textile printing, for office, home applications or graphics applications, such as for paper goods, for example, for ballpoint pens, felt tips, fiber tips, card, wood, (wood) stains, metal, inking pads or inks for impact printing processes (with impact-pressure ink ribbons), for the preparation of 5 colorants for coating materials, for industrial or commercial use, for textile decoration and industrial marking, for roller coatings or powder coatings or for automotive finishes, for high-solids (low-solvent), water-containing or metallic coating materials or for pigmented formulations for aqueous paints, for the preparation of pigmented plastics for coatings, fibers, platters or mold carriers, for the preparation of 10 non-impact-printing material for digital printing, for the thermal wax transfer printing process, the ink jet printing process or for the thermal transfer printing process, and also for the preparation of color filters, especially for visible light in the range from 400 to 700 nm, for liquid-crystal displays (LCDs) or charge combined devices (CCDs) or for the preparation of 15 cosmetics or for the preparation of polymeric ink particles, toners, dye lasers, dry copy toners liquid copy toners, or electrophotographic toners, and electroluminescent devices. The following examples illustrate various embodiments of the invention, but the scope of the 20 invention is not limited thereto. The microwave generator used was a CEM Discover@ model, with a circular single mode cavity design, that focuses the microwave radiation on the sample. The sample was contained in a sealed glass tube, whereby the pressure was allowed to increase to a 25 maximum of 20.69 e 10 5 Pa (300 p.s.i.). The maximum operating power of this device was 300 watts. 1 H and 13 C NMR spectra were obtained at 300 and 75 MHz respectively, and coupling constants are in Hz. Mass spectral measurements were obtained using chemical ionisation at 70 eV, with isobutane as carrier gas.
WO 2005/005430 PCT/EP2004/051259 19 Examples Example I CO Et O 2 /HN HN 0 OH 1 2-2 5 3,6-Diphenylfuro[3,4.c]pyrrole-1,4-dione (2) Ethyl 4-benzoyl-4,5-dihydro-5-oxo-2-phenylpyrrole-3-carboxylate 1 (99.5 mg, 0.296 mmol, prepared as previously reported in W003022848) was irradiated with microwave radiation (at a frequency of 2 to 45 GHz, and a forward power of 300 Watts) without solvent, heating to 250 *C for 10 minutes. The crude product was then allowed to cool, methanol was added and 10 the solid filtered off and washed with methanol. This gave the furopyrrole 2 as an orange solid (73 mg, 86 %). Decomp > 300 *C. 8H (DMSO d 6 ) 11.87 (1 H, s, NH), 8.12 - 8.23 (4H, dm, Ar-H) and 7.48 - 7.54 (6H, m, Ar-H); 8c (DMSO d 6 ) 161.4, 159.3 (2 x C=O), 152.2, 148.1 (2 x quat.), 132.8, 132.6, 129.1 (2C), 128.0, 127.0 (6 x Ar C-H), 126.8, 126.4, 115.8, 102.8 (4 x quat.). 15 Comparative Example I (Example 1 of W003022848) A mixture of ethyl 4-benzoyl-4,5-dihydro-5-oxo-2-phenylpyrrole-3-carboxylate 1 (10 g, 0.0299 mol) and Dowtherm A (200 ml) was heated to 230-240 *C under nitrogen for 64 h. The solution was then cooled to 25 *C and added dropwise to petrol ether 40-60 (300 ml) upon 20 which a fluorescent orange solid precipitated. This was filtered off, washed with further hexane and dried in vacuo. Yield 3.48 g (40 %).
WO 2005/005430 PCT/EP2004/051259 20 Example 2
CO
2 Et
CO
2 Et 0 HN + 0 HN - HN 0 4 CI NOH Br 0 S Br Br 0 0 Me-N N - Me-N 0 o 0 7 Br Br 5 a) p-Bromobenzoyl Chloride (3) p-Bromobenzoic acid was purified by dissolving in NaOH (aq) and washing the solution with dichloromethane, followed by acidification of the aqueous layer with dilute aqueous HCI, and extraction with EtOAc. The acid (4.00 g, 0.0182 mol), oxalyl chloride (4.634 g, 3.185 ml, 0.0364 mol), and a catalytic amount of DMF was stirred overnight at room temperature in 10 DCM (40 ml). Evaporation of the solvents and excess reagents gave the acid chloride 3 as an off-white solid. m.p. 38-40 0 C. b) Ethyl 4-(p-bromobenzoyl)-4,5-dihydro-5-oxo-2-phenylpyrrole-3-carboxylate (5) To sodium hydride (590 mg, 14.75 mmol) was added THF (40 ml), and the pyrrolinone ester 15 4 (852 mg, 3.69 mmol). After stirring for 30 mins at room temperature, a solution of p bromobenzoyl chloride (809.5 mg, 3.69 mmol) in THF (10 ml) and a catalytic amount of DMAP, was added and the mixture was stirred at room temperature overnight. 10 % HCI (aq) was added, and the organic component extracted with diethyl ether. Concentration in vacuo and recrystallisation from ethanol gave the enol 5 as a yellow crystalline solid (665 mg, 44 20 %). M.p. 189 *C; 3H (DMSO d- 6 ) 11.90 (1H, s, NH), 7.72 - 7.82 (2H, m, ArH), 7.58 -7.66 (4H, m, ArH), 7.42 - 7.53 (3 H, m, ArH), 3.72 (2H, q, CH 2
CH
3 ) and 0.9 (3H, t, CH 2
CH
3 ); m/z 416 WO 2005/005430 PCT/EP2004/051259 21 (M+1 1 Br, 100 %), 414 (M+1 79 Br, 96 %) 347, 319, 317, 296 c) 3-(p-Bromophenyl)-6-phenyl furo[3,4-c]pyrrole-1,4-dione (6) The p-bromobenzoylpyrrolinone ester 5 (154 mg, 0.37 mmol) was irradiated with microwave 5 radiation (at a frequency of 2 to 45 GHz, and a forward power of 300 Watts) without solvent, heating to 250 *C for 10 minutes. The crude product was then allowed to cool, methanol was added and the solid filtered off and washed with methanol. This gave the furopyrrole 6 as a red solid (129 mg, 94 %). M.p. 295 *C (subl., decomp.); 8H (DMSO de) 11.88 (1H, s, NH), 8.13 - 8.17 (2H, m, Ar-H), 7.98 and 7.66 (2 x2H, AA'BB', J 8.7, C 5
H
4 ) and 7.43 - 7.47 (3H, 10 m, Ar-H); m/z 370 (M+1 81 Br, 94 %) and 368 (M+1 79Br, 100 %). d) 5-Methyl-3-(p-bromophenyl)-6-phenylfuro[3,4-c]pyrrole-1,4-dione (7) A mixture of furopyrrole 6 (1.5 g, 4.08 mmol), methyl tosylate (1.14 g, 6.12 mmol), potassium carbonate (1.13 g, 8.16 mmol) and dimethylformamide was stirred at room temperature 15 overnight. Water was then added, and the organic component extracted with DCM. The solvent was removed, and washing with water then methanol gave the methylated compound 7 as a red solid (0.831 g, 53 %), m.p. 215-216 *C. 5H (CDCI 3 ) 8.19 and 7.61 (each 2H, AA'BB', p-C 6
H
4 Br), 7.78-7.73 (2H, m, o-Ph), 7.54-7.50 (3H, m, rn/p-Ph) and 3.38 (3H, s,
NCH
3 ). Amaw (abs) (DCM)/nm 454 (E 15,878) 20 a) 2--iethyl-5-ph(nyl-6-(p-Bromophenyl)-3-phenylpyrrolo[3,4-c)pyrrole-1,4-dione () A mixture of furopyrrole 7 (300 mg, 0.79 mmol), aniline (146 mg, 1.57 mmol), DCC (323 mg, 1.57 mmol), trifluoroacetic acid (2-3 drops) and DCM was stirred at room temperature for 144 hours. The solvent was removed, and washing with methanol gave the pyrrolopyrrole 8 as a 25 red solid (173 mg, 55 %), m.p. 255-256 *C. 8H (CDC] 3 ) 7.88-7.83 (2H, m, Ar-H), 7.49-7.43 (5H, m, Ar-H), 7.40-7.26 (5H, m, Ar-H), 7.12-7.07 (2H, m, Ar-H) and 3.35 (3H, s, NCH 3
)
WO 2005/005430 PCT/EP2004/051259 22 Example 3
CO
2 Et
CO
2 Et HN + HN - - HN 0 9 OH 0 00 -10 0 2 N 11 12
NO
2
NO
2 0 0 Me-N N Me-N 0 14 %7 13
NO
2 NO 2 a) Ethyl 4.-(p-nitrobenzoyl)-4,5-dihydro-5-oxo-2-phenylpyrrole-3-carboxylate (11) 5 The pyrrolinone ester 9 (6.35 g, 27.5 mmol) was added to a mixture of sodium hydride (2.0 g, 82.5 mmol) and THF (1 litre), and this was stirred at room temperature for 15 minutes. p Nitrobenzoyl chloride 10 was then added, and the mixture was stirred overnight. Methanol was added, followed by water and the mixture acidified with HCL. The organic component was extracted with diethyl ether and the solvent evaporated. Washing with methanol gave 10 the nitro compound 11 as a yellow solid (6.31 g, 60 %). 8H (DMSO-de) 11.95 (1H, s, NH), 8.30 and 7.84 (each 2H, AA'BB', Ar), 7.56-7.50 (2H, m, 0-Ph), 7.45-7.35 (3H, m, m/p-Ph), 3.62 (2H, q, OCH 2
CH
3 ) and 0.75 (3H, t, OCH 2
CH
3 ). m/z (ESI -ve) 380 (22 %, M 4 ), 379 [100 %, (M - 1)]* 15 b) 3-(p-Nitrophenyl)-6-phenylfuro[3,4-c]pyrrole-1,4-dione (12) The p-nitrobenzoylpyrrolinone ester 11 (300 mg, 0.90 mmol) was irradiated with microwave radiation without solvent, heating to 270 *C for 15 minutes. The crude product was then allowed to cool, methanol was added and the solid filtered off and washed with methanol. This gave the furopyrrole 12 as a red solid (230 mg, 87 %). 20 6H (DMSO-d 6 ) 12.15 (1H, s, NH), 8.38 (4H, s, p-C 5
H
4 N0 2 ), 8.34 - 8.28 (2H, m, o-Ph) and 7.69 - 7.58 (3H, m, m/p-Ph). m/z (ESI -ve) 334 (21 %, M*), 333 [100 %, (M-1)] * WO 2005/005430 PCT/EP2004/051259 23 c) 5-Methyl-3-(p-nitrophenyl)-6-phenylfuro[3,4-c]pyrrole-1,4-dione (13) A mixture of furopyrrole 12 (0.9 g, 2.7 mmol), methyl tosylate (750 mg, 4.04 mmol), potassium carbonate (1 g, 7.2 mmol) and dimethyl formamide was stirred at room 5 temperature overnight. Water was then added, and the organic component extracted with DCM. The solvent was removed, and washing with water then methanol gave the methylated compound 13 as a red solid (0.652 g, 70 %), m.p. 253-255 *C. 8H (CDC 3 ) 8.55 and 8.38 (4H, AA'BB', Ar), 7.88-7.84 (2H, m, o-Ph), 7.65-7.60 (3H, m, m/p-Ph) and 3.49 (3H, s, NCH 3 ). Amax (abs) (DCM)/nm 482 ( 17,462) 10 d) 2-Methyl-5'-phenyl-6-(p-nitrophenyl)-3-phenylpyrrolo[3,4-c]pyrrole-1,4-dione (14) A mixture of furopyrrole 13 (100 mg, 0.29 mmol), aniline (53 mg, 0.57 mmol), DCC (118 mg, 0.57 mmol), trifluoroacetic acid (2-3 drops) and DCM was stirred at room temperature for 72 hours. The solvent was removed, and washing with methanol gave the pyrrolopyrrole 14 as a 15 red solid (63 mg, 52 %), m.p. 233-235 C. 6H (CDCl3) 8.16 and 7.81 (each 2H, AA'BB', p
C
6
H
4
NO
2 ), 7.98-7.93 (2H, m, o-Ph), 7.60-7.55 (3H, m, m/p-Ph), 7.44-7.36 (3H, m, m/p-Ph), 7.20-7.15 (2H, m, o-Ph) and 3.45 (3H, s, NCH 3 ). AMax (abs) (DCM)/nm 493 (e 14,014) WO 2005/005430 PCT/EP2004/051259 24 Example 4 /\N NH 0 21 O CO 2 Et /
C
2 Et N 2 O0H 0 0 15 0 16 17 0 0 N N N O O / a) Ethyl 4,5-dihydro-5-oxo-1,2-diphenylpyrrole-3-carboxylate (16) 5 Aniline (2.65 g, 2.59 ml, 0.0285 mmol) was added to a solution of ethyl 5-oxo-2-phenyl-4,5 dihydro-furan-3-carboxylate 15 (made via the literature method described in F. Gaudemar Bardone, M. Mladenova, R. Couffignal, Synthesis, 1985, 1043) (6.0 g, 0.0259 mmol) and acetic acid (100 ml), and the solution heated to reflux for 3 hours. The solution was then cooled, diluted with water and extracted with diethyl ether. The organic extracts were dried 10 and concentrated. Column chromatography (silica gel, eluent dichloromethane) gave the lactam 16 as a colourless solid (6.9 g, 87 %), m.p. 129-130 *C. 8 H (CDCl 3 ) 7.32-7.15 (8H, m, Ar-H), 6.98-6.93 (2H, m, o-Ph-N), 4.08 (2H, q, OCH 2
CH
3 , J 6.9), 3.67 (2H, s, CH 2 ) and 1.11 (3H, t, OCH 2
CH
3 , J 6.9) 15 b) Ethyl 4-benzoyl-4,5-dihydro-5-oxo-1,2-diphenylpyrrole-3-carboxylate (17) A solution of pyrrolinone ester 16 (1.76 g, 5.74 mmol) in tetrahydrofuran (100 ml) was cooled WO 2005/005430 PCT/EP2004/051259 25 to -78 *C, and a 1.0 M solution of lithium hexamethyldisilazide (17.2 ml, 17.2 mmol) in THF was added. After 5 minutes, benzoyl chloride (0.97 g, 0.79 ml, 6.89 mmol) was added, and the solution stirred for 30 mins. Methanol was added, and the solution warmed to room temperature. The mixture was acidified (aqueous HCI) and extracted with diethyl ether. The 5 ether extracts were dried and concentrated. Column chromatography (silica gel, eluent dichloromethane) gave the enol 17 as a yellow solid (1.74 g, 74 %), m.p. 137-139 *C. SH (CDCl 3 ) 7.75-7.68 (2H, m, Ar), 7.54-7.44 (3H, m, Ar), 7.34-7.19 (8H, m, Ar), 7.14-7.07 (2H, m, Ar), 3.54 (2H, q, CH 2 , J 7.2) and 0.65 (3H, t, CH 3 , J 7.2) 10 c) 3,5,6-triphenyl-1 H-furo[3,4-c]pyrrole-1,4(5H)-dione (18) Benzoyl pyrrolinone ester 17 (74 mg) was irradiated with microwave radiation (at 300 Watts) without solvent, heating to 200 *C for 10 minutes. The crude product was then allowed to cool, methanol was added and the solid filtered off and washed with methanol. This gave the furopyrrole 18 as an orange solid (34 mg, 52 %), m.p 230-232 *C (lit. [H. Langhals, T. 15 Grundei, T. Potrawa, K. Polborn, Liebigs Ann. Chem., 1996, 679] 230-232 *C). 8H (CDC 3 ) 8.48-8.42 (2H, m, Ar-H) and 7.61-7.20 (13H, m, Ar-H) d) 2,3,5,6-Tetraphenyl-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (19) Can be prepared starting from the intermediate 18 as described in H. Langhals, T. Grundei, 20 T. Potrawa, K. Polborn, Liebigs Ann. Chem., 1996, 679. a) 2,3,6-triphanylpyrrolo[3,4-c]pyrrole-1,4-dione (21) N-phenyl pyrrolinone ester 16 (663 mg, 2.16 mmol) and benzonitrile (446 mg, 440 pl, 4.3 mmol) were added successively to a solution of sodium t-amyl oxide [from sodium (150 mg, 25 6.5 mmol) and t-amyl alcohol (4.0 ml)], and the mixture heated to reflux for 6 hours. The mixture was then cooled, and acidified (dilute aqueous HCI) and extracted with dichloromethane. The organic extracts were then dried and the solvent evaporated. Precipitation from methanol, followed by filtration gave the triphenyl pyrrolopyrrole 21 as a bright orange solid (18 mg, 3 %), m.p. 390 *C (decomp). 8 H (DMSO d 6 ) 11.54 (1 H, s, NH), 30 8.55 (2H, m, Ar-H), 7.57-7.67 (5H, m, Ar-H), 7.38-7.54 (6H, m, Ar-H), 7.29-7.33 (2H, m, Ar H); m/z (LCMS) 363.96 (30%, M), 362.95 (100 %, M-H); Am,, abs (DMSO)/nm 269 (E /24,550), 303 (15,720) 470 (22,580) and 498 (23,640)
Claims (8)
1. A process for the preparation of furopyrroles of the general formula A 0 A3-N 0 (1), comprising O A 2 5 (a) heating a compound of the formula A 1 CO 2 R Au-N OH (11) under microwave irradiation optionally in the presence of an O A 2 inert solvent, wherein A' and A 2 are Cl-C 18 alkyl, C 2 -C 1 salkenyl, C 2 -C 1 8 alkynyl, C5-C 8 cycloalkyl, C 5 Cscycloalkenyl, aryl or heteroaryl, 10 A 3 is hydrogen, C-C 1 aalkyl, cyanomethyl, Ar, -CR 30 R 31 -(CH 2 )m-Ar 3 or Y-R 32 , wherein R 3 0 and R 31 independently of each other stand for hydrogen or C-C 4 alkyl, or phenyl which can be substituted up to three times with C-C 4 alkyl, ArP stands for aryl, C 5 -Cacycloalkyl, C 5 -Cacycloalkenyl or heteroaryl, which can be substituted one to three times with C-C 8 alkyl, C-Cealkoxy, halogen or phenyl, which 15 can be substituted with C-C 8 alkyl or CI-C 8 alkoxy one to three times, and m stands for 0, 1, 2, 3 or 4, R is C-C 1 aalkyl, in particular C-C 4 alkyl, aryl, in particular phenyl, or aralkyl, in particular benzyl, which can be substituted one to three times with C-C 8 alkyl, C C 8 alkoxy, or halogen, 20 Y is -C(O)-, -C(0)0-, -C(O)NH-, -SO 2 NH- or -SO 2 - and R 3 2 is C-C 18 alkyl, Ar 3 , or aralkyl.
2. The process according to claim 1, comprising in addition WO 2005/005430 PCT/EP2004/051259 27 reacting a compound of formula I with a primary amine of the formula A 4 -NH 2 (IV), A 0 wherein a DPP of formula A3--N N-A formula IlII is obtained, 0 A 2 wherein A 4 is C-C 8 alkyl or Ar 3 , wherein Ar, A', A 2 and A 3 are defined as in claim 1. 5 3. The process according to claim 1, wherein the compound of the formula I, wherein A 3 is different from a hydrogen atom, is obtained by reacting a compound of the formula A4 O H-N 0 (la) with a compound of the formula A -X (V), wherein A', A 2 and 20 O A2 A 3 have the meanings as given in claim 1 and X is a leaving group. 10 4. The process according to any of claims 1 to 3, wherein A' and A 2 are radicals of the formula R R 2 B R 2 , _N, R5 R 4 0 or G R 3 , wherein R 6 R 1 and R 2 are independently of each other hydrogen, halogen, CI-C1,alkyl, C 15 C 18 alkoxy, C-C 1 alkylmercapto, Cl-C 1 8 alkylamino, Cl-C 1 salkoxycarbonyl, C C 18 alkylaminocarbonyl, -CN, -NO 2 , trifluoromethyl, C 5 -Cecycloalkyl, -C=N- WO 2005/005430 PCT/EP2004/051259 28 (C-C 18 alkyl), phenyl, -C=N /R3 , imidazolyl, pyrrazolyl, triazolyl, piperazinyl, pyrrolyl, oxazolyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, morpholinyl, piperidinyl or pyrrolidinyl, -CONX 5 X 6 , -C(O)OX 7 or -S0 2 X 9 ; wherein X 5 and X6 are hydrogen, linear or branched C 1 . 1 0 -alkyl, C6. 1 0 -cycloalkyl or CO. 1 0 -aryl, X 7 is 5 hydrogen, linear or branched C 1 _ 1 0 -alkyl, C5. 1 0 -cycloalkyl or C. 10 -aryl, X 9 is hydrogen, linear or branched C 1 . 1 0 -alkyl, Cs. 10 -cycloalkyl, C 7 . 1 0 -aralkyl, C 6 . 1 Q-aryl or -NX 0 X", wherein X 10 and X" are hydrogen, linear or branched C 1 . 1 o-alkyl, C 7 .. 1-aralkyl or Cs.10 aryl, G is -CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -, -CH=N-, -N=N-, -0-, -S-, -SO-, -S0 2 -, -SO 2 NH-, 10 -CONH- or -NR R 3 and R4 are independently of each other hydrogen, halogen, C-Cealkyl, C-C 18 alkoxy or -CN, R 5 and R 6 are independently of each other hydrogen, halogen or C 1 -C 6 alkyl, and R 7 is hydrogen or C 1 -Cralkyl; or radicals of the formula R26 25 R250 R15 26 2 R R R
7-_26 R 25 R R 21 N N2 RR RR N R3 RN 2 21 23R21C 1 23 15 RR WO 2005/005430 PCT/EP2004/051259 29 -R -R R 21 N R 2 2 23 R N R RR R R 21 23 2 R R '3 2 2 R 2 3 R. 25N R 2 1R2 26 RR 2 5 RR R 2 6 or R 2 R 24 N R 26 5 wherein R 21 , R 22 , R 2 , R 2 5 and R 2 e are independently of each other hydrogen, C Csalkyl, a hydroxyl group, a mercapto group, C-C 8 alkoxy, Cl-Cealkylthio, halogen, halo-C-Csalkyl, a cyano group, an aldehyde group, a ketone group, a carboxyl group, an ester group, a carbamoyl group, an amino group, a nitro group, a silyl group or a 10 siloxanyl group and R 24 is a C-C 6 alkyl group. 5. The process according to claim 4, wherein A' and A 2 are radicals of the formula WO 2005/005430 PCT/EP2004/051259 30 R N / ~N, / '~or R2 R4 G R 3 wherein R 1 and R 2 are independently of each other hydrogen, chloro, bromo, Ce-C 4 alkyl, Cl-Cralkoxy, Cl-Cealkylamino, phenyl or CN, 5 G is -0-, -NR-, -N=N- or -S02-, R 3 and R 4 are hydrogen, and R 7 is hydrogen, methyl or ethyl. 6. The process according to claim 4 or 5, wherein A 3 is cyanomethyl, C 1 -Cealkyl such as 10 methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-buty, isobutyl, tert.-butyl, n-pentyl, 2 pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, Y-R 32 wherein Y is -C(O)- and R 3 2 is / 0 \ R 40 , wherein R 40 is C-C 4 alkyl, -0-Cl-C 4 alkyl, or -S-C-C 4 alkyl, or -(CH 2 )m-Ar wherein m is 1 and Ar is a group of the formula 15 , or which can be substituted one to three times with C-C 8 alkyl, Cl-Cealkoxy, halogen or phenyl. 7. The process according to any of claims 4 to 6, wherein A 4 is 20 or which can be substituted one to three times with C-C 8 alkyl, C-Cealkoxy, halogen or phenyl. WO 2005/005430 PCT/EP2004/051259 31
8. The process according to any of claims I to 7, wherein the starting compound of formula (II) A4 CO 2 R A-N OH 0 A 2 5 (II) is obtained by reacting a compound of formula (Vill) with an acyl halide A 2 -COX: A 1 CO 2 R A CO 2 R A COX A N A A 3 -N OH 0 A 2 (Vill) (II) wherein R, A' and A 2 have the same meaning as given in claim 1, A 3 is aryl, and X is 10 halogen, preferably chlorine.
9. The process according to claim 8, wherein the compound of formula (Vill) is obtained by reacting a compound of formula (1Ib) with an amine A 3 -NH 2 : A 1 CO 2 R A 1 CO 2 R A-NH 2 O 0 15 (11b) (Vill) wherein R and A' have the same meaning as given in claim I and A 3 is aryl
10. The process according to claim 8 or 9, wherein A 2 _COX is benzoyl chloride and A 3 -NH 2 is aniline. 20
11. A process for the preparation of a DPP of general formula: WO 2005/005430 PCT/EP2004/051259 32 A 1 O AA- N N H (111), comprising A 2 reacting a compound of formula (Vill) with a nitrile A 2 -CN, preferably benzonitril: A 1 A 1 0 CO 2 R N t-AmONa A 3 -N + t-AmOH A 3 -N NH A 2 o O A 2 5 wherein A', A 2 and A 3 have the meanings as given in claim 1.
12. A DPP of general formula (Ill) A 1 0 A3-N NH 0 A 2 10 wherein A', A 2 and A 3 have the meanings as given in claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03405507 | 2003-07-07 | ||
| EP03405507.9 | 2003-07-07 | ||
| PCT/EP2004/051259 WO2005005430A2 (en) | 2003-07-07 | 2004-06-28 | Process for the preparation of furopyrroles |
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| AU2004255863A1 true AU2004255863A1 (en) | 2005-01-20 |
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| AU2004255863A Abandoned AU2004255863A1 (en) | 2003-07-07 | 2004-06-28 | Process for the preparation of furopyrroles |
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| EP (1) | EP1641802A2 (en) |
| JP (1) | JP4745226B2 (en) |
| KR (1) | KR20060033780A (en) |
| CN (1) | CN1816553A (en) |
| AU (1) | AU2004255863A1 (en) |
| TW (1) | TW200504077A (en) |
| WO (1) | WO2005005430A2 (en) |
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| WO2002095361A2 (en) * | 2001-05-22 | 2002-11-28 | President And Fellows Of Harvard College | Identification of anti-protozoal agents |
| NZ548212A (en) * | 2003-12-29 | 2010-07-30 | Sepracor Inc | Pyrrole and pyrazole DAAO inhibitors |
| EP1904066B1 (en) | 2005-07-06 | 2018-05-23 | Sunovion Pharmaceuticals Inc. | COMBINATIONS OF ESZOPICLONE AND TRANS 4-(3,4-DICHLOROPHENYL)-1,2,3,4-TETRAHYDRO-N-METHYL-1-NAPTHALENAMINE OR TRANS 4-(3,4-DICHLOROPHENYL)-1,2,3,4-TETRAHYDRO-1-NAPTHALENAMINE, for treating MENOPAUSE, perimenopause AND COGNITIVE DISORDERS |
| KR101381768B1 (en) * | 2006-01-06 | 2014-04-07 | 선오비온 파마슈티컬스 인코포레이티드 | Tetralone-based monoamine reuptake inhibitors |
| JP5432526B2 (en) | 2006-01-06 | 2014-03-05 | サノビオン ファーマシューティカルズ インク | Cycloalkylamines as monoamine reuptake inhibitors |
| AU2007233041B2 (en) | 2006-03-31 | 2013-05-02 | Sepracor Inc. | Preparation of chiral amides and amines |
| US20080058395A1 (en) * | 2006-06-30 | 2008-03-06 | Sepracor Inc. | Fused heterocyclic inhibitors of D-amino acid oxidase |
| US7884124B2 (en) * | 2006-06-30 | 2011-02-08 | Sepracor Inc. | Fluoro-substituted inhibitors of D-amino acid oxidase |
| US7579370B2 (en) * | 2006-06-30 | 2009-08-25 | Sepracor Inc. | Fused heterocycles |
| US7902252B2 (en) * | 2007-01-18 | 2011-03-08 | Sepracor, Inc. | Inhibitors of D-amino acid oxidase |
| JP2010516697A (en) * | 2007-01-18 | 2010-05-20 | セプラコール インク． | D-amino acid oxidase inhibitor |
| NZ580429A (en) | 2007-05-31 | 2012-04-27 | Sepracor Inc | Phenyl substituted cycloalkylamines as monoamine reuptake inhibitors |
| US20100120740A1 (en) * | 2008-08-07 | 2010-05-13 | Sepracor Inc. | Prodrugs of fused heterocyclic inhibitors of d-amino acid oxidase |
| WO2011017634A2 (en) * | 2009-08-07 | 2011-02-10 | Sepracore Inc. | Prodrugs of fused heterocyclic inhibitors of d-amino acid oxidase |
| JP6162984B2 (en) * | 2013-03-14 | 2017-07-12 | 山本化成株式会社 | Thermosensitive color-forming composition and thermosensitive recording material using the composition |
| CN105038767B (en) * | 2015-06-29 | 2017-04-26 | 北京理工大学 | Fluorescent reagent for detecting trichloromethane in air as well as preparation method and application thereof |
| CN106279188A (en) * | 2016-07-21 | 2017-01-04 | 青岛科技大学 | A kind of preparation method of furane derivative also [2,3 b] azole derivatives |
| CN107338459B (en) * | 2017-07-25 | 2018-11-16 | 上海新阳半导体材料股份有限公司 | Leveling agent, the metal plating compositions containing it, preparation method and application |
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| US4931566A (en) * | 1987-07-31 | 1990-06-05 | Ciba-Geigy Corporation | Process for the preparation of pyrrolo[3,4-c]pyrroles |
| KR0143777B1 (en) * | 1989-11-28 | 1998-07-01 | 월터 클리웨인, 한스-피터 위트린 | Compositions of Materials Based on Diketopyrrolopyrrole |
| EP0511165B1 (en) * | 1991-04-26 | 1996-08-14 | Ciba-Geigy Ag | Dicetopyrrolopyrrole compounds |
| JP3641310B2 (en) * | 1994-12-22 | 2005-04-20 | チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド | Electrophotographic photoreceptor |
| TW341572B (en) * | 1995-09-20 | 1998-10-01 | Ciba Sc Holding Ag | Preparation of mixed crystals and solid solutions of 1,4-diketopyrrolopyrroles |
| DE59707889D1 (en) * | 1996-01-30 | 2002-09-12 | Ciba Sc Holding Ag | Polymerizable diketopyrrolopyrroles and polymers made therewith |
| US5919944A (en) * | 1997-07-30 | 1999-07-06 | Ciba Specialty Chemicals Corporation | Polymerisable diketopyrrolopyrroles |
| TW503255B (en) * | 1999-09-27 | 2002-09-21 | Ciba Sc Holding Ag | Electroluminescent devices comprising diketopyrrolopyrroles |
| JP2002201401A (en) * | 2001-01-09 | 2002-07-19 | Konica Corp | Pigment dispersion, and ink for ink jet |
| ATE310775T1 (en) * | 2001-05-14 | 2005-12-15 | Ciba Sc Holding Ag | NEW CRYSTAL MODIFICATION OF A SOLID SOLUTION OF A DIKETOPYRROLOPYRROLE PIGMENT |
| DK1436296T3 (en) * | 2001-09-11 | 2006-07-17 | Ciba Sc Holding Ag | Process for direct preparation of pyrrolo [3,4-c] pyrroles |
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| US20070100135A1 (en) | 2007-05-03 |
| KR20060033780A (en) | 2006-04-19 |
| EP1641802A2 (en) | 2006-04-05 |
| WO2005005430A3 (en) | 2005-06-16 |
| CN1816553A (en) | 2006-08-09 |
| JP2009513534A (en) | 2009-04-02 |
| WO2005005430A2 (en) | 2005-01-20 |
| TW200504077A (en) | 2005-02-01 |
| US7442804B2 (en) | 2008-10-28 |
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